Quaternary ammonium sulfone halides



Patented Jan.

OFFICE uuazrnnuamr AMMONIUM SULFONE mamas 1.1.1.... L. Linch, Wilmington, net, as... to

E. I. du Pont de Nemours 8: Company, Wilmlngton, Del., a corporation of Delaware No Drawing. Application April Serial N0. 532,529

cum. (cl. zoo-s s) This invention relates to a new class of organic quaternary ammonium compounds and more particularly refers to quaternary ammonium sulfone halides and processes for their production and use,

This application is a continuation in part of my copending application Serial No. 451,682 filed on July 20, 1942, and bearing the same title, now Patent No. 2,359,863.

It is an object of this invention to produce a new class of organic quaternary ammonium compounds having particular value as surface-active agents, textile agents, auxiliary agents in making fungicides, insecticides, waterproofing agents, and as. intermediatesin the production of the aforesaid compounds, as well as in the production of dyes, pharmaceuticals and related products. A further object is to produce a new class of quaternary ammonium compounds comprising quaternary ammonium sulfone halides. Additional objects will become apparent from a consideration of the following description and claims.

These objects are attainedin accordance with the present invention wherein quaternary ammonium sulfone halides are produced and employ d as hereinafter described. In a more re-.

stricted sense this invention is concerned with quaternary ammonium sulfone chlorides, particularly those conforming to the following formula:

may together form a heterocyclic ring.) X represents an anion, particularly an anion of a strong acid.

In a still more restricted embodiment this invention is directed to quaternary ammonium sulfone halides having the following formula:

wherein R and R represent hydrocarbon groups,

X represents an anion of a strong acid, and Y represents a halogen atom.

A In its preferred embodiment this invention is concerned with compounds conforming to the general formula just described wherein Y represents chlorine, particularly compounds such as N-chloro N-trimethyl amino ethane sulfone chloride.

Compounds of the aforementioned type may be produced by various methods. For instance, an organic sulfonic acid containing as a substituent a pentavalent nitrogen atom, unsubstituted by hydrogen, may be condensed with halogenating agents such as phosphorous pentachloride, chloro sulfonic acid, and the like. In this reaction some heating is usually advisable in order to carry it to completion. An inert diluent is frequently helpful, although it may be omitted. Likewise, an amount of one of the reactants in excess of that required for the reaction may be employed in order to reduce the fusion point of the reaction mixture. Condensation is customarily carried out under atmospheric pressure and the product recovered by decantation, filtration, etc.; or the excess halogenating agent and by-products may be removed by lowering the pressure on the reaction vessel.

' In place of the foregoing general process it is also to be understood that a sulfone halide group may be introduced into a quaternary ammonium derivative capable of sulfonation. This reaction is conducted along similar lines to that mentioned previously, except the sulfone halide group is introduced into the compound rather than the halogen atom alone. In this reaction the quaternary ammonium substituted derivative may be mixed with a halogeno sulfonic acid either directly or in the presence of inert diluents, and heat applied, if necessary, until reaction is complete. The desired reaction product may be separated from the remaining components of the reaction mixture in the usual manner.

The invention may be more readily understood by a consideration of the following illustrative examples wherein the quantities are stated in parts by weight.

EXAMPLE 1 N-chloro N-trimethyl amino ethane sulfone chloride f Twenty-five parts of N-trimethyl amino ethane sulfonic acid inner anhydride (prepared by con- .fonic acids and their derivatives in general can 3. Trimethyl ammonium bromo cetane sulzionate I 3 densing beta-bromo-ethane sodium 'sulionate ionic acid. the corresponding phenyl benzyl diwithltrimethylamineinmethyl alcohol at 160 C.) methyl ammonium sulfate sulione bromide or is mixed with 49.2 parts of phosphorus pentafluoride is obtained. Other inert solvents suchas chloride. Reaction begins at once and the mixcarbon tetrachloride, orthodichlorobenzene, dioxture is rapidly reduced to a viscous syrup with 5 ane, nitrobenzene, kerosene, etc., produce equally the evolution of heat. The reaction mixture is good results. .1

heated to 115 C.. allowing the P osphorus oxy- The above method tor the manufacture oi chloride to distill oil. The temperature is held quaternary ammonium sulione halides is appliat nil-115 C.'ior one hour; then the pressure is cable in general to derivatives susceptible of sulreduced on the reaction vessel to remove last ronation. The following compounds are a reptraces of volatile by-products. A nearly quantiresentativerew oi the many which may be treated tative yield 01' N-chloro N-trimethyl amino in accordance with this invention:

ethane sulfone chloride is recovered after drying in vacuo. C1

In a similar manner. N-substitution and C-sub= stitution products of quaternary ammonium 8111- I rz-wrma 01GB: be converted to the corresponding quaternary ammonium sulione chlorides or bromides. The following compounds are a representative i'ewoi 2 the quaternary suli'onic acids and derivatives which may be treated in accordance with this invention:

' GHKOMa-N-Olla-OIh-AO:

- in): 2. (CH1)3N-CHz-ONH-OHr-CHr-SO:H (030 0.3 CH:- -OHr-ONH so (obtained by bromlnation or cetene sulionic acid followedby a reaction with trimethylamine). 4. Dimethyl cetyl ammonium butane sulfonate.

(CHQr- OHr-CHCl-S0:Na

CHt-CH-Q-OH Br- (CR3 mai-i-oH-N:

Exam: 2 I

Pheny'l benzyl dimethyl ammonium sulfate Br suljone chloride c-cHr-i!r(cisi)3 (EH02 i r A However, the methods for the preparation 01 aryl quaternary ammonium suli'on chloride is not cm confined to the use of chiorosulfonlc acid as a r l chlguii'osulfonating agent with aryl quaternary ammo um derivatives. Equally good results are ob- A0411 socl tained by condensing aryl quaternary ammonium v sulfonic acids with agents, such as phosphorus pentachloride, usually employed in producing sulty Parts f phenyl b yl dimetbylmpmo fone halides. For example, dimethyl phenyl Ilium chloride (pr pared by condensing benzyl parasulfobenzyl ammonium chloride (prepared chl ride with di Bi y1 n1 e in 81001101) 18 8118- by condensing parachloromethyl benzene sulfonic p ded in 2 parts of tetrachloroethanei t acid with dimethyl anyline) heated with phosnine parts of chlorosulionic acid is run into this phorus pentachloride yields t correspondin su pe i n u r ood agitation during 10 methyl Phenyl benzyl ammonium chloride sulutes time interval. The reaction is exothermic fone 1 ,1

and hydrogen chloride is released. The mixture is heated to 56 C. during 1% hours and held at (0H9? 56-62 c. for 1% hours. The mixture is cooled 11H; to room temperature and the two liquid phases C1 Pcll separated. The lower solvent layer is discarded, on!

or used in a subsequent chlorination. The product is freed of solvent under vacuum on a steam (c1192 bath. A theoretical yield of phenyl benzyl di- 4 i methyl ammonium sulfate sulfone chloride is obc1 P0 no] tained as an oil. By substituting bromosulfonic om acid or fluorosulionic acid in place or chloro-sulor anhydro para-sulfophenyl trlmethyl ammonium chlorid yields para-chloro-sulfonyl phenyl trimethyl ammonium chloride, 1. e.,

Aryl derivatives containing more than one group capable of undergoing conversion to sulfonyl and/or carbonyl chlorides in the presence ofan excess of thionyl chloride, phosphorus pentachloride,etc. yield poly'acid chloride derivatives, 1. e.,

-cn Cl 2P0 orr I '01 2POCh 2301 It is to ,be understood that the foregoing examples are illustrative merely of a representative few of the many modifications to which this invention is susceptible. They may be varied widely with respect to the individual reactants, the' amounts thereof and the conditions of reaction without departing from the scope hereof.

Temperatures in the range of 80 C. to 150 C. are generally employed, although this range is not critical. Temperatures within the range of room temperature to 100 C. are preferred for the majority of reactions.

not used. For this purp'ose, pressures other than atmospheric pressure are sometimes helpful.

The amount 'of halogenating agent employed to convert the quaternary ammonium compound to the corresponding acid chloride may be varied within 'wide limits above the stoichiometric amounts required. It is, however, usually advisable to use from 10% to 50% excess-halogenating agent in order to assure completion of the reaction and to compensate for mechanical losses and hydrolysis due to contact with the atmosphere. It is, of course, to be understood that if more than one acid group is present on the quaternary ammonium compound more than one molecular equivalent of halogenating agent will be required in order to obtain complete conversion of the acid groups to the corresponding acid chlorides. Complete conversion of acid groups is of course not always essential and if desired some unconverted acid groups may be permitted to remain on the reaction product or in the reaction mixture.

When the sulfone halide group is introduced into the quaternary ammonium compounds it is generally advisable to employ two molecular equivalents of a halogeno-sulfonic acid for each sulydroxide heated with phosphorus pentai fone halide group which is to be introduced. This is particularly true where dehydrating agents are not employed in the reaction, as the by-product, water, produced,- hydrolyzes part of the halogeno-sulfonic acid. A large excess of halogenssulionic acid will ordinarily result in the introduction of morethan one sulfon e halide group.

Where reference is made herein to the term "halogen atom or halide it is understood to define the atoms chlorine, bromine or fluorine. Chlorine is the preferred halogen atom and the examples hereof havebeen primarily directed to the introduction of such atom into the desired compounds. However, in its stead either bromine or fluorine may be employed by suitable changes in the reactants.

By means of the present invention a new class of quaternary ammonium compounds, particularly adapted for employment in the industrial arts,

has been discovered. These compounds are.es

pecially suitable for use as intermediates insolubilizing existing compounds and synthesizing old compounds. Likewisethey are of particular value as intermediates for the production of dyes, pharmaceuticals, insecticides, fungicides, bactericides, surface-active agents, textile agents, auxiliary agents in the manufacture of paper, resist agents for vatprinting and other printing agents, waterproofing agents, corrosion inhibitors, etc. So far as known, these quaternary ammonium compounds and those referred to in the parent application are the only materials which can be used for the synthesis of quaternary ammonium substituted acid halide addition compounds with primary, secondary or tertiary amines. Many of these water-soluble addition compounds exhibitunusual properties. These compounds are likewise of value in the production of esters, amides,

'.and other derivatives substituted by pentavalent nitrogen which is unsubstituted by hydrogen.

As many apparently widely different embodi- .ments' of this invention may be made without fined in the appended claims.

I claim: 1. A quaternary ammonium sulione resented by the following formula:

halide repwherein R represents a member selected from the (CHrh-N-CIELq-CHr-S 01C] 4. A quaternary ammonium resented y the following formula:

wherein R represents a member selected from the sulfone halide rep- 1 sents chlorine.

v7 a class consisting oi ethylene, phenylene and benzylene radicals, R1 and R2 represent alkyl radicals containing less than eight carbon atoms, 3: represents a member selected from the class consisting of alkyl radicals of less than eighteen carbon atoms, phenyl and benzyl radicals, X represents an anion or a strong acid, and Y represents a halogen atom. I

5. The products oi claim 4 wherein Y repre- ADRIAN 1. men.

REFERENCES CITED The following references are of record in the me of this patent:

OTHER REFERENCES Gabriel et. al., Ber. Dent Chem. Vol. 44, p9 sass-sass (1911). 

